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The phosphines PPh,,(CH,CH,CH=CH,)3-n, n = 2-0, PPh,,(CH,CH2CH2CH=CH2),-,,, n = 1 or 2, and PPh,CH,CH=CH, have been synthesized and studied by ' H and ,'P magnetic resonance. The n.m.r. spectra of PPh,(OCH,CH=CH2), its oxide, O=PPh,(OCH,-CH=CH,), and its Arbuzov rearrangement product, 0=PPh2(CH2CH=CH2), have been investigated by ,'P decoupling of the proton spectrum, selective proton decoupling of the ,'P spectrum, and comparison with computer-simulated spectra to determine the spin-spin coupling constants. The n.m.r. spectra of the related oxides O=PPh,CH,CH,CH=CH,, O=P-(CHZCH2CH=CH2),, and O=P(OCH,CH=CH,), are also assigned. The data indicate that ,JPH > ,JpH for alkenylphosphines, 2Jp,, is larger for phosphine oxides than for phosphines, and ,Jell is little changed in comparing phosphorus(II1) with phosphorus(V) compounds.On a synthktise les phosphines PPh,,(CH2CH2CH=CH2),-,,, ti = 2-0,

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The interaction of carbon d isu I phide with d i -7-cyclopentadienylva nadium (I I), en neacarbo nyldii ron (0) , potassium pentacyanocobaltate(il), and cyclo-octa-l,5-dienechloroiridium( I) leads to complexes where carbon disulphide is co-ordinated to the metal by both carbon and sulphur atoms or, in the cobalt complex, as a bridge group -Co-SC(S)Co-.The complexes are characterised, interalia, by infrared (i.r.), and for (n-C5H5),VCS2, by electron spin resonance (e.s.r.) spectra.The interaction of tris(triphenylphosphine)chlororhodium(l) with carbon disulphide in presence of excess of triphenylphosphine and methanol, produces the first example of a thiocarbonyl (CS) complex, trans-bis(tripheny1phosphine)thiocarbonylchlororhodium( I). This complex and the corresponding bromide can be oxidised by halogen to the octahedral complexes RhX3(CS) (PPh3)2. The mode of formation of the thiocarbonyl complex is discussed briefly.( a ) A I .

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